TW200832019A - Liguid crystal alignment agent and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent, which maintains the voltage holding ratio while reducing accumulated charges and further has outstanding printability. The liquid crystal alignment agent comprises a compound as shown in following general formula (1). (Wherein, A and B are individually hydrogen atom or glycidyl group, R1-R4 are individually hydrogen atom or glycidyl group, X is a group having two valence bonds as shown in following formula (X1) or (X2), Y is a group having two valence bonds as shown in following formula (Y1), (Y2) or (Y3). (Wherein, R5-R14 are individually hydrogen atom, alkyl group, alkoxyl group or alkyl group comprising fluorine, Z is a group having two valence bonds expressed by -O-, -NH-, -CH2-, -SO2-, -C(CH3)2- or -C(CF3)2-.))

Description

200832019 IX. Description of the Invention: TECHNICAL FIELD The present invention relates to a liquid crystal alignment agent and a liquid crystal display element for forming a liquid crystal alignment film of a liquid crystal display element. More specifically, the present invention relates to a liquid crystal alignment agent capable of forming a liquid crystal alignment film having good electrical properties and excellent printability, and a liquid crystal display element using the same. [Prior Art] At present, as a liquid crystal display element, a TN type liquid crystal display element having a so-called TN (T wistedr, k Nematic) type liquid crystal cell is known, which is formed of polylysine on the surface of a substrate provided with a transparent conductive film. A liquid crystal alignment film made of a polyimine or the like is used as a substrate for a liquid crystal display element, and two substrates are opposed to each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form an interlayer. The unit cell of the structure, the long axis of the liquid crystal molecules is continuously twisted by 90 degrees from one substrate to the other substrate. Further, STN (Super Twisted Nematic) type liquid crystal display elements and vertical alignment type liquid crystal display elements having higher contrast and smaller viewing angle dependence than TN type liquid crystal display elements have been developed. The STN type liquid crystal display element uses a liquid crystal in which a chiral agent as an optically active substance is blended in a nematic liquid crystal as a liquid crystal by using a long axis of liquid crystal molecules to be continuously twisted by more than 180 degrees between substrates. The birefringence effect produced by the state. In contrast, as disclosed in Non-Patent Document 1 and Patent Document 1, a vertical alignment type liquid crystal display element called MVA (Multi Domain Vertical Alignment) type in which protrusions are formed on a transparent conductive film to control a liquid crystal alignment direction is proposed. . The liquid crystal display element of the MVA type is excellent not only in the viewing angle but also in the ratio of 200832019, and also in the process of forming the liquid crystal alignment film, which is not required to be rubbed, and is excellent in the process. As a liquid crystal alignment film suitable for the TN, STN, and MVA systems, it is required that the residual image erasing time of the liquid crystal display element is short. Further, as an alignment agent for forming these liquid crystal alignment films, it is required to have excellent printability in lithography. [Non-Patent Document 1] "Liquid Crystal" Vol. 3 No. 2 1 1 7 (1 999) [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. [Patent Document 3] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei No. 5 - 1 07 5 No. 4 [Patent Document 4] Japanese Patent Laid-Open Publication No. Hei 5 No. 1 07 5 44 [Non-Patent Document 2] K. Hasegawa, Polymer Journal. Vol. 31, No. 2,206 (1 9 99) [Patent Document 5] Japanese Laid-Open Patent Publication No. 2000-4468-3 [Patent Document 6] International Publication No. 2002/00 00949 [Invention] The present invention In view of the above problems, it is an object of the invention to provide a liquid crystal alignment agent which has a reduced charge charge while maintaining a voltage holding ratio and which has excellent printability, and a liquid crystal display element using the same. Other objects and advantages of the invention will be apparent from the description which follows. The above object of the present invention, first, is achieved by a liquid crystal alignment agent (hereinafter referred to as "first liquid crystal alignment agent") containing a compound represented by the following formula (1), 200832019 R1 \ N-Y-N R2 i X-

R3

N—Y~Ni, B

(wherein, A and B are each independently a hydrogen atom or a glycidyl group, and R1 to R4 are each independently a hydrogen atom or a glycidyl group, and X is a divalent group represented by the following formula (XI) or (X2); ,

(X1)

(X2) Y is a divalent group represented by the following formula (Yl), (Y2) or (Y3), 200832019

(wherein R5 to R14 are each independently a hydrogen atom, an alkyl group, an alkoxy group or a fluorine-containing alkyl group, and Z is a mono-, a-NH-, a CH2-, a S-2-, a C-CH3 2—or a divalent group represented by C(CF3)2—). The above object of the present invention, and secondly, is achieved by a liquid crystal alignment agent (hereinafter referred to as "second liquid crystal alignment agent") which contains a compound represented by the following general formula (1 ') and a tetracarboxylic dianhydride. Polylysine,

200832019 (wherein A, B, X and γ are the same as the above formula (1), and R1 to R4 are a hydrogen atom). The above object of the present invention is, in a third aspect, achieved by a liquid crystal display device comprising a liquid crystal alignment film formed of any one of the above liquid crystal alignment agents. [Embodiment] The first liquid crystal alignment agent of the present invention contains the compound represented by the above formula (1). ^ In the above formulae (Y1) to (Y3), R5 to R14 are each independently a hydrogen atom f \ , an alkyl group, an alkoxy group or a fluorine-containing alkyl group. As the above-mentioned base, a hospital base having a carbon number of 1 to 6 is preferable, and specific examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, and a 2-methyl group. Propyl, 3-methyl-propyl, n-pentyl, n-hexyl and the like. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, and a n-butoxy group. Base, 2-methyl-propoxy, 3-methyl-propoxy, n-pentyloxy, n-hexyloxy and the like. Examples of the fluorine-containing alkyl group include a -CF3 group, a CH2CF3 group, and a CF2CF3 group. R5 to R14 in the above formula are preferably a hydrogen atom, a methyl group, an ethyl group or a CF3 group. Further, Z in the above formula (Y2) is a divalent group represented by mono-, one-NH-, one-CH2-, ～S〇2-, one C(CH3)2- or -C(CF3)2-. Preferably, it is mono-, one-NH-, one-CH2-, one C(CH3)2- or one C(CF3)2-. -10- 200832019 In the above formula (1), A, B, X, Y and R1 to R4 may be used in any combination of preferred groups. Among the compounds represented by the above formula (1), particularly preferred are the compounds of the following (A) or (B). (A) In the above formula (1), Y is a compound of a divalent group represented by the above formula (Y1) or (Y2). (B) In the above formula (1), A and B are each a hydrogen atom, and R1 to R4 are each independently a hydrogen atom or a glycidyl group, but at least one of R 1 to R 4 is a glycidyl group. Preferred specific compounds represented by the above formula (1) include the following compounds. -11- 200832019

-12- 200832019

-13- 200832019

OMSMO

OMSno

3 Y 3 Η - Η clcic

/\

£

CO ϊ 3 FI F CIC1C

The table of the carboxylic acid dicarboxylic acid of the dianhydride dicarboxylic acid is the same as the table of the chemical composition of the compound \i/ shown in the table (1 丨 (the above formula is obtained from the inclusion of the agent to the acid amine) /X or X)/ A Γ\ The following is a combination of the possible properties of the product. The compounding of the compound-14- 200832019 (A' ) In the above formula (1'), Y is the above formula ( a compound of a divalent group represented by Y1) or (Y2). (Β') A compound of the above formula (1') wherein hydrazine and hydrazine are hydrogen atoms. Preferred specific compound represented by the above formula (1 ') The following compounds can be mentioned.

-NH 2 h2n-〇-nh"〇~〇-nhhQ^

OM^WUO clolc

CF3丨 i 丨CF

OMSno

3 1 3 F I F ??c

-15- 200832019

ΟΠ&ΜΟ

Onsno

3 T 3 F - F clcic

3 1 3 F 1 F C—C—C

The tetracarboxylic dianhydride which can be used when the compound represented by the above formula (1 ') is reacted with a tetracarboxylic dianhydride to synthesize polyamic acid, and 1,2,3,4-cyclobutane tetracarboxylic acid is mentioned. Dihydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4 ,5,9b-hexaoxy-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]furan-1,3-dione, cis-16 - 200832019 Formula 3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetradecanoic acid dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2 :3,5:6-dianhydride, l,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)- Naphthalene [1,2-〇:]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4·dione-6-spiro-3'-(tetrahydrofuran-2' , 5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5, 6-Tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0'6]undecane. ^", ... - tetraketone to pyromellitic dianhydride, etc. These acid anhydrides may be used alone or in combination of two kinds of r and \. The compound represented by the above formula (1 ') and tetracarboxylic acid. When the acid dianhydride is reacted to synthesize polyglycine, another diamine may be used together with the compound represented by the above formula (1 '). Preferred other diamines which can be used herein may, for example, be - Phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 2,2'-dimethyl-4,4'-diaminobiphenyl 1,5-Diaminonaphthalene, 2,7-diaminoguanidine, 9,9-dimethyl-2,7-diaminoguanidine, 4,4'-diaminodiphenyl ether, 2 ,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9·'bis(4-aminophenyl)anthracene, 2,2-di[4-(4-amino) Phenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylphenyldiisopropylidene)diphenylamine, 4, 4'-(m-phenylphenyldiisopropylidene)diphenylamine, 1,4-cyclohexanediamine, 4,4'-methylbis(cyclohexylamine), 1,4-bis(4) -aminophenoxy)benzene, 4,4 - bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine , 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6- Diaminocarbazole, N,N,-bis(4-aminophenyl)-benzidine, -17· 200832019 N,N'-bis(4-aminophenyl)-N,N'-dimethyl Further, these other diamines may be used alone or in combination of two or more. When other diamines are used together with the compound represented by the above formula (1 '), the amount of other diamines is used. The total amount of the compound represented by the above formula (1) and the other diamine is preferably 50% by weight or less. The polyamine derivative of the compound represented by the above formula (1 ') and the tetracarboxylic dianhydride The method for synthesizing polylysine which is one of the optional components of the liquid crystal alignment agent of the present invention can be carried out in the same manner as the method described below. The liquid crystal alignment agent of the present invention contains the compound represented by the above formula (1) or the above. Formula (1 ') means The polyamic acid obtained by reacting a compound with a tetracarboxylic dianhydride is an essential component, but may further contain a polyamic acid selected from the group consisting of a repeating unit represented by the following formula (I-1) and having a lower At least one of the group consisting of polydentimine of the repeating unit represented by the formula (I-2), an adhesion promoter, etc., /HO〇a.COOH \ (J (1-1) - V-HNOC CONH —Q14-

200832019 (wherein P2 is a tetravalent organic group and Q2 is a divalent organic group). The polyamic acid having the repeating unit represented by the above formula (I-1) can be synthesized by a reaction of a tetracarboxylic dianhydride and a diamine, and the polyimine having the repeating unit represented by the above formula (1 to 2) can be passed. A polyglycine having a repeating unit of pi of P2 and Q1 of Q2 in the above formula (I) is dehydrated and closed. The tetracarboxylic dianhydride used in the synthesis of the polyamic acid having the repeating unit represented by the above formula (I-1) may, for example, be an alicyclic tetracarboxylic acid anhydride or an aliphatic tetracarboxylic acid. Anhydride, aromatic tetracarboxylic dianhydride, and the like. Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1,2,3,4-ring. Butane tetracarboxylic dianhydride, 1,3 -dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3 -dichloro-1,2,3,4-cyclobutane Alkanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid Dianhydride, iota, 2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutyl ring Oct-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarbonyl-2-carboxyl Norbornane-2:3,5:6-dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3&,4,5,91)-hexahydro-5-( Tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91)-six Hydrogen-5-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&amp ;,4,5,913-hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-(:]-furan-1,3- Diketone, 1,3,3&,4,5,91)- Hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3, 3&,4,5,913-hexahydro-7-ethyl-5-(tetra-19-200832019 hydrogen-2,5-dioxo-3-furanyl)-naphthalene[1,2 · c]-furan- 1,3 -dione, 1,3,33,4,5,91 hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l, 2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo-3- Furyl)-naphthalene [1,2-(:]-furan-1,3-dione, l,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(four Hydrogen-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuranmethylene)- 3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3- Oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro) -3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane stomach 2:3,5:6- Dihydride, 4,9-dioxatricyclo[5.3.1.0''6]undecane-3,5,8,10-tetraketone, the following formula I) and compound (II), or the like,

(wherein R15 and R17 represent a divalent organic group having an aromatic ring, R1 and R18 represent a hydrogen atom or an alkyl group, and a plurality of R16 and R18 which are present may be the same or different). -20-200832019 The above-mentioned aliphatic tetracarboxylic dianhydride may, for example, be butane tetracarboxylic acid dianhydride. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, and 3,3',4,4'- Biphenyl sulfonium tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4' - Biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonane tetracarboxylic acid Dihydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)r, diphenyl sulfide dianhydride, 4,4' - Bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3', 4, 4'-Perfluoroisopropylidenedicarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid Anhydride, di(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride , bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylbenzene) Formic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-di(hydroper trimellitate), propylene glycol-di(dehydrated trimellitate), 1,4-butanediol - bis (dehydrated trimellitate), 1,6-hexanediol-di (anhydrotrimellitic acid ester), 1,8-octanediol-di (dehydrated trimellitate), 2, 2 - bis(4-hydroxyphenyl)propane-di(hydrogen trimellitate), a compound represented by the following formula (2) to (5), and the like. -21 - 200832019

, CH3, ch3 (3)

Among the tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydride is preferably 1,2,3,4--22-200832019 cyclobutane from the viewpoint of satisfactory liquid crystal alignment. Tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4 - cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-di Oxotetrahydrofuran methylene)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, cis-3,7-dibutylcyclooctane-1,5-diene-1 , 2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2:3,5:6-dianhydride, 1,3,3&,4,5 , 9^ hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]furan-1,3-dione, 1,3,3& 4,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]furan-1,3-di Ketone, 1,3,3&,4,5,91)-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l ,2-c]furan-1,3-dione, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1 Octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)- 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4,9- Dioxatricyclo[5.3.1.0''6]undecane-3,5,8,10-tetraketone, a compound represented by the following formula (6) to (8) in the compound represented by the above formula (I) Or a compound represented by the following formula (9) in the compound represented by the above formula (II). -23- 200832019

i.

Particularly preferred are 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride. 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3&,4,5,913-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-called furan-1,3-dione, cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3 ,5,6-tricarbonyl-2-carboxynorbornane-2:3,5:6-dianhydride, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(four Hydrogen-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]furan '1,3-diketone, 3-oxabicyclo[3.2.1]octane-2,4- Diketo-6-spiro-3'-(tetrahydrofuran-2',5'dione), 5-(2,5- -24-200832019 dioxotetrahydro-3.furanyl)-3-methyl 3-cyclohexene-1,2-::: citrate liver, 3,5,6-tricarboxy-2-carboxyl-norbornane-2: 3,5:6-dianhydride, 4,9 · two Oxabicyclo[5.3.1.02,6]undecane-3,5,8,10-tetraketone, and a compound represented by the above formula (6), particularly preferably 2,3,5-tricarboxycyclopentyl Acetic acid dianhydride. Further, preferred examples of the aliphatic tetracarboxylic dianhydride and the aromatic tetracarboxylic dianhydride include butane tetracarboxylic dianhydride, pyromellitic dianhydride, and 3,3', 4, 4'. - benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylindole tetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 1, 4,5,8-naphthotetradecanoate dioxime I anhydride. These tetracarboxylic dianhydrides may be used singly or in combination of two or more. When only one type is used, it is preferred to use an alicyclic tetracarboxylic dianhydride. When two or more types are used in combination, the alicyclic tetracarboxylic dianhydride is preferably used in an amount relative to the entire tetracarboxylic dianhydride. The amount used is 50% by mole or more. The diamine used in the synthesis of the polyamic acid having the repeating unit represented by the above formula (I-1) may, for example, be an aromatic diamine, an aliphatic or an alicyclic diamine. A hydrazine-based amine group and a diamine, a diamine-based organoaluminoxane or the like in addition to a nitrogen atom other than the hydrazine-based amine group. Examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 4,4,-diaminodiphenylmethane, and 4,4,-diaminodiphenylethane. 4,4,-Diaminodiphenyl sulfide, 4,4,-diaminodiphenylanthracene, 2,2,-dimethyl-4,4,-diaminobiphenyl, 3,3 ,-Dimethyl-4,4'-diaminobiphenyl, 4,4,-diaminobenzimidamide, 4,4,-diaminodiphenyl ether, 1,5-diamino Naphthalene, 2,2,-ditrifluoromethyl-4,4'-diamino-based, -25- 200832019 3,3'-ditrifluoromethyl-4,4'-diaminobiphenyl, 5. Amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 6-amino-1-(4'-aminophenyl)-1,3, 3-trimethylindan, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4' - Diaminobenzophenone, 2,2·bis[4-(4·aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexa Fluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl] maple, 1,4-di(4- Aminophenoxy)benzene, 1,3-bis(4-aminophenoxyl) Benzo, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl M0- ί: 4 hydroquinone, 2,7-diamino fluorene, 9 , 9-dimethyl-2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 2, 2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino- 5,5'-dimethoxybiphenyl , 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4'-(p-phenylphenylisopropylene)diphenylamine, 4,4'- -phenylphenylisopropylene)diphenylamine, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-di Amino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, etc. Examples of the aliphatic or alicyclic diamine include 1,1-m-xylylenediamine, 1,3-propylenediamine, butanediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, and octane. Diamine, decane diamine, 4,4-diaminoheptyldiamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene diamine, hexahydro-4 ,7-methylene dimethylene Diamine, tricyclo[6.2.1.02'7]-undecene dimethyldiamine, 4,4'-methylenebis(cyclohexylamine), etc. as the above-mentioned molecule having two first-order amine groups and Examples of the diamine of a nitrogen atom other than the amine group of the first-stage amine group include, for example, 2,3-diaminopyridin-26-200832019 pyridine, 2,6-diaminopyridine, and 3,4-diamino group. Pyridine, 2,4-diamine-based chelate D, 5.6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyrimidine D, 2,4 -diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis(3-aminopropyl)pyridazine, 2,4-diamino-6-isopropyl Oxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1, 3,5-trisyl, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino 2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diamine-based hip-hop,

5.6-Diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxylated Lactic acid ester, 3,8-diamino-6-phenylphenanthrene, 1,4-diaminopyridazine, 3,6-diaminoacridine, bis(4-aminophenyl)benzene Amine, 3,6-diaminocarbazole, oxime-methyl-3,6-diaminocarbazole, oxime-ethyl-3,6-diamine, squat,]\1-phenyl- 3,6-Diamino, yesterday, ^, ^^['-bis(4-aminophenyl)-benzidine, anthracene, Ν'-bis(4-aminophenyl)·Ν,Ν' Dimethyl-benzidine, etc. In addition, as the above-mentioned diamine organooxane, a compound represented by the following formula (10), and the like, R21 R21 (10) H2N-fCH2^-卞 姑CH ΝΗ7ΝΗ2 R21 R21 (wherein R21 represents a hydrocarbon group having 1 to 12 carbon atoms. A plurality of R21 groups may be the same or different, and Ρ is an integer of 1 to 3, and q is an integer of 1 to 2 0). These diamines may be used alone or in combination of two or more. Among these diamines, p-phenylenediamine, 4,4'-diaminodiphenyl-27-200832019 alkane, 4,4'-diaminodiphenyl sulfide, 2,2'-di are preferred. Methyl 4,4'-diaminobiphenyl, 1,5-diaminonaphthalene, 2,7-diaminopurine, 9,9-dimethyl-2,7-diaminopurine, 4 , 4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2, 2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene) Diisopropylidene)diphenylamine, 4,4'-(m-phenylene diisopropylidene)

Aniline, 1,4-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine), 1,4-bis(4-aminophenoxy)benzene, 4,4'-di (4 -aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6 -diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminoguanidine Azole, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-indole, Ν'-dimethyl-benzidine. When the liquid crystal alignment agent of the present invention has a pretilt performance performance, it is preferred that a part or all of the diamine used in the synthesis of the polyamic acid having the repeating unit represented by the above formula (I-1) has the following formula ( Q - 1) or a diamine of the structure represented by the following formula (Q-2) (hereinafter, referred to as "specific diamine"),

(Q-1) (wherein, Ζ is a single bond, -〇-, -C〇-, -C〇〇-, -〇C〇-, -NHCO-, -C〇NH-, -S- or An aryl group, R19 is an alkyl group having a carbon number of 10 to 20, a monovalent organic group having an alicyclic skeleton having a carbon number of 4 to 40, or a fluorine-containing monovalent organic group having a carbon number of 6 to 20. ), -28- 200832019 Z————z

(Q-2) (wherein Z is a single bond, -〇-, -CO-, -C〇〇-, -〇C〇-, -NHC〇-, -C〇NH-, -S- or The aryl group, R2° is a divalent organic group having an alicyclic skeleton having a carbon number of 4 to 40). Thus, a part or all of the group Q1 and the group Q2 in the above formula (1 - 1) can be a group of the structure represented by the above formula (Q - Π or (Q - 2), thereby giving it a performance pre In the above formula (Q-1), the group having a carbon number of 丨0 to 20 represented by R19 may, for example, be n-decyl, n-dodecyl, n-pentadecyl or n. The six-yard base, the positive eight-yard base, the positive ten-yard base, etc. In addition, the carbon number represented by R19 in the above formula (Q-1) and R2° in the above formula (Q-2) is 4 to 40. The organic group having an alicyclic skeleton may, for example, be a group having an alicyclic skeleton derived from a cycloalkane such as cyclobutane, cyclopentane, cyclohexane or cyclodecane; having cholesteric and cholesteric a group having a steroid skeleton such as decyl alcohol; a group having a bridged alicyclic skeleton such as norbornene or adamantane; and particularly preferably a group having a steroid skeleton. The organic group may also be a group substituted by a halogen atom (preferably a fluorine atom) or a fluoroalkyl group (preferably a trifluoromethyl group). The fluorine atom-containing group having 6 to 20 carbon atoms represented by R19 in the above formula (Q-1) may, for example, be a straight bond of n-hexyl, n-octyl or n-decyl group having a number of 6 or more. An alicyclic hydrocarbon group having 6 or more carbon atoms such as a cyclohexyl group or a cyclooctyl group; and a hydrogen atom of an organic group such as an aromatic hydrocarbon group having 6 or more carbon atoms such as a phenyl group or a biphenyl group; Or three -29- 200832019 chloromethyl% chlorophenyl group-substituted groups. In addition, Z in the above formula (Q-1) and the above formula (Q-2) is a single bond, -〇-, -C〇 -, -COO- ' -〇C〇-, -NHC〇-, -C〇NH-, -S_ or an aryl group. Examples of the aryl group include a phenyl group, a tolyl group, and a phenyl group. Further, as a specific example of the diamine having a structure represented by the above formula (Q-1), for example, dodecyloxy-2,4-diaminobenzene or pentadecyloxy group can be mentioned. 2,4·diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, represented by the following formulas (11) to (15) Compounds, etc.

30-200832019 Specific examples of the diamine having a structure represented by the above formula (Q-2) include, for example, a compound represented by the following formulas (16) to (18). These specific diamines may be used alone or in combination of two or more.

Among these specific diamines, preferred are the compounds represented by the above formula (11), (13), (15) or (16). The ratio of use of the specific diamine to the total amount of the diamine varies depending on the magnitude of the pretilt angle to be expressed, and in the case of the TN type or STN type liquid crystal display element, it is preferably 〇5 to 5 mol%. In the case of the vertical alignment type liquid crystal display element, it is preferably 5 to 100% by mole. The acid anhydride group of one equivalent of the amine-tetracarboxylic dianhydride of the synthetic diamine to which the polyaminic acid having the repeating unit represented by the above formula (I-1) is supplied is preferably a ratio of 0.2 to 2 equivalents. Good for 0 · 3 ~ 1 · 2 equivalent ratio. The synthesis reaction of polylysine is preferably carried out in an organic solvent at -20 ° C to 150 ° C, more preferably at a temperature of 〇 1 ° ° C, preferably -31 - 200832019 1 0 minutes ~ 5 0 hours, more preferably for 30 minutes ~ 3 0 hours. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid, and examples thereof include 1-methyl-2-pyrrolidone, anthracene, fluorene-dimethylacetamide, hydrazine, and hydrazine. - dimethylformamide, 3-butoxy-oxime, Ν-dimethylpropanamide, 3-methoxy-oxime, Ν-dimethylpropanamine, 3-hexyloxy-oxime, Amidoxime solvent such as hydrazine-dimethylpropionamide; aprotic polar solvent such as dimethyl hydrazine, r, butyrolactone, tetramethylurea or hexamethylphosphonium triamine; A phenolic solvent such as phenol, xylenol, phenol or halogenated phenol. The amount of the organic solvent (^) is usually preferably such that the total amount of the tetracarboxylic dianhydride and the diamine compound (/3) is 〇. 1 to 30 by weight relative to the total amount of the reaction solution (α + /3 ). The amount of %. In the range in which the produced polyamine acid is not precipitated, a part of the organic solvent as described above may also be a poor solvent of polylysine, an alcohol, a ketone, an ester, an ether, or a halogen. Replacement of hydrocarbons, hydrocarbons, etc. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, and 1,4 - Glycol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, Butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether , ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, two Glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether-32- 200832019 acetate, tetrahydrofuran , dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, two Toluene, isoamyl propionate, isobutyric acid Amyl, diisoamyl ether. The amount of the poor solvent which can be used herein is preferably 50% by weight or less, more preferably 40% by weight or less, based on the total amount of the solvent. As described above, a reaction solution in which polylysine was dissolved was obtained. Then, the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate, and the precipitate can be dried under reduced pressure or the reaction solution can be distilled off under reduced pressure with an evaporator to obtain a polyamine. Further, the polyproline is re-dissolved in the organic solvent, and then the polyamine acid can be purified by a process of precipitating with a poor solvent once or several times or by distillation under reduced pressure using an evaporator. The polyimine having the repeating unit represented by the above formula (I-2) can be obtained by dehydrating and ring-closing polylysine having a repeating unit of the above formula (I-丨) wherein p1 is p2 and Q1 is Q2. In the case of dehydration ring closure, the proline structure may be dehydrated and closed to form a quinone ring, or only a part of the proline structure may be dehydrated and closed to form a polymer having a guanidine structure and a quinone ring structure. As the polyimine which can be used in the present invention, the ratio of the repeating unit having a quinone ring (hereinafter referred to as "deuterated imidization ratio") is preferably 40 mol% or more with respect to all the repeating units. Good is 50% or more. By using a polymer having a ruthenium iodide ratio of 40 mol% or more, a liquid crystal alignment agent capable of forming a liquid crystal alignment flue having a short afterimage erasing time can be obtained. The ruthenium amination rate can be determined by the following method. -33- 200832019 Determination of oxime imidization ratio of ruthenium iodide H After drying the ruthenium iodide polymer under reduced pressure at room temperature, in the case of dimethyl sulfoxide, tetramethyl decane The reference material was determined by 1H-NMR and determined by the formula shown in the following (ii). Ruthenium amination rate (%) = (1 - AVA2xa)xl〇〇---- A1 : peak area of protons derived from NH group (i〇ppm) A2 : peak area derived from other protons, α : ratio of the number of other protons of protons of 1 in the precursor of the polymer (polyproline). The dehydration ring closure of polylysine may be carried out by (i) heating by a polyhydrazine method, or (ii) by dissolving polyglycine in an organic solvent, adding a dehydrating agent and a dehydration ring-closure catalyst, and heating as needed. The reaction temperature in the above method (i) for heating poly-proline is 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is insufficient, the dehydration ring-closure reaction cannot be completed completely. If the reaction temperature exceeds 3, the molecular weight of the obtained ruthenium-imided polymer is preferably decreased from 10 minutes to 5 hours, more preferably 30 minutes. 3 On the other hand, in the case of the method of the above polychlorinated acid solution and the dehydration ring-closure catalyst in the above (ii), an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride is used as the dehydration. The amount, depending on the desired hydrazine imidization ratio, is preferably 0.01 to 2 moles relative to the repeating unit of valine. As the dehydrating agent, for example, a method in which pyridine, trimethylpyridine, or dimethyl port is dissolved in the direction of (ii) NH-amino acid at room temperature is preferably used, and preferably 50 Å. C, ® 200. . , condition. The reaction is small. A de-agent can be added, and the dehydrogenating agent can be catalyzed by a 1 molar polymerization ring-blocking catalyst such as pyridine or triethyl-34-200832019-based fee. However, it is not limited to these. The amount of the dehydration ring-closing catalyst is preferably 〇 1 1 1 1 1 相对 relative to the dehydrating agent used in 1 mol. The higher the amount of the above dehydrating agent and the dehydration ring-closing catalyst, the higher the ruthenium amination rate. Further, as the organic solvent used in the dehydration ring-closure reaction, an organic solvent exemplified as a solvent used in the synthesis of polylysine may be mentioned. Further, the reaction temperature of the dehydration ring closure reaction is preferably 〇~1 8 〇 ° C, more preferably 10 0 to 150 ° C. The reaction time is preferably from 30 minutes to 10 hours, more preferably from 1 hour to 7 hours. The obtained polyimine can be purified by subjecting the reaction solution thus obtained to the same operation as in the purification method of polylysine. The polyaminic acid having the repeating unit represented by the above formula (I-1) or the polyimine having the repeating unit represented by the above formula (I-2) may also be a terminal-modified polymer having a molecular weight adjusted. By using the terminal-modified polyglycolic acid or polyimine, the coating properties and the like of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. Such a terminally modified polyamic acid or polyimine can be synthesized by adding a monobasic acid anhydride, a monoamine compound, a monoisocyanate compound or the like to the reaction system in the synthesis of polyamic acid. Among them, examples of the monobasic acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl group. Succinic anhydride and the like. Further, examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, and the like. N-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, n-t-35-200832019 Amines, etc. Further, as the monoisocyanate compound, phenyl cyanate or naphthyl isocyanate may be used.

In the case of the poly-10% solution having the repeating amine acid represented by the above formula (I-1) or the repeating unit represented by the above formula (I-2), preferably having a composition of 20 to 800 mPa, Preferably, the polymer has a viscosity of 30 to 500 mPa.s. Further, the solution viscosity (mPa's) of the polymer is measured by using E Γ at 25 ° C for a solution diluted to a solid concentration of 10%. When the liquid crystal alignment agent of the present invention is a polyaminic acid having a repeating unit having the above formula or a polyimine having the above formula (I-2), the ratio of use thereof is 1 part by weight for the first liquid crystal. The compound represented by the above formula (1) is preferably the following, more preferably 10 to 500 parts by weight. Further, the poly-proline which is obtained by reacting the chemical &acid dianhydride represented by the above formula (1') with respect to 1 part by weight of the first agent is preferably 100 to 80 parts by weight. The liquid crystal alignment agent of the present invention preferably contains both polylysine having a repeating unit represented by 1) and polyamidiamine having a repeating unit of the above formula (). In this case, the above formula (poly unit of repeating unit) The total amount of the amine acid and the polyamidene represented by the above formula (I-2) is preferably a polyamine derivative having a repeating unit represented by the above formula (I-1) within the above range (I - 2) The use of the polyimine of the repeating unit represented by t. For example, a poly-imine of a different unit, a solvent of a polystyrene at a viscosity of s, a rotational viscosity of the type: (I-1) represents a repeat a single alignment agent, a phase of 100 parts by weight of a liquid crystal alignment compound and a tetracarboxylic component or less, and a repeating unit represented by the above formula (I-t-2), which is represented by 1 to 1). The total amount of the polyacetic acid having the repeating unit represented by the above formula (I-1) and the polyimine having the repeating unit represented by the above formula (I-2) with respect to -36 - 200832019 The polyamine amount of the repeating unit represented by the above formula (I-1) is preferably used in an amount of 5 0 to 95% by weight, more preferably 55 to 90% by weight. Polylysine having a repeating unit represented by the above formula (I-1) and polyimine having a repeating unit represented by the above formula (I-2) Preferably, each is a polymer synthesized from a tetracarboxylic dianhydride containing 2,3,5-tricarboxycyclopentylacetic acid dianhydride and a diamine. In this case, 2,3,5-tricarboxycyclopentane The amount of the acetic acid dianhydride to be used is preferably 50% by mole or more based on the total amount of the tetracarboxylic dianhydride. The above-mentioned adhesion improving agent may, for example, be a compound containing a functional decane or a formula (1) or a formula. An epoxy compound other than the compound represented by (1'). The functional decane-containing compound may, for example, be 3-aminopropyltrimethoxydecane or 3-aminopropyltriethoxydecane, 2 -Aminopropyldimethoxylate, 2-aminopropyltriethoxylate, Ν-(2.Aminoethyl)_3-aminopropyltrimethoxydecane, Ν-(2 -aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl- 3- Propyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecyl Propyltriethylamine, 10-trimethoxydecyl-1,4,7-triazadecane, 1 〇-triethoxydecyl-1,4,7-triazaindene Alkane, 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl- 3-Aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxy-37-200832019 decane, N-phenyl-3-aminopropyltrimethoxydecane, N- Phenylpropyltriethoxydecane, N-bis(oxyvinyl)-3-aminopropyldecane, N-bis(oxyvinyl)-3-aminopropyltriethoxydecane as formula (1) And a compound other than the compound represented by the formula (1 '), for example, ethylene glycol diglycidyl ether, polyethylene diglyceryl ether, propylene glycol diglycidyl ether, tripropylene glycol dihydrate polypropylene glycol diglycidyl ether, new Pentyl glycol diglycidyl ether alcohol diglycidyl ether, glycerol diglycidyl , 2,2-dibromo neoglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-EN,N,N',N'-tetraglycidyl-xylylenediamine, 1,3-Diglycerylaminomethyl)cyclohexane, N,N,N',N'-tetra--4,4'-diaminodiphenylmethane, N,N-diglycidyl Glycidyl-aminomethylcyclohexane, 3-(N-allyl-N-yl)aminopropyltrimethoxydecane, 3-(N,N-diglycidyltrimethoxydecane Wait. The use ratio of the adhesion promoter as described above is 40 parts by weight or less, more preferably 0.1 to 30 parts by weight, per 100 parts by weight of the compound represented by the above formula (1). Further, the liquid crystal alignment agent is preferably used in an amount of from 0.1 to 25 parts by weight, based on 100 parts by weight of the polyamic acid obtained by reacting the compound of the above formula (1 with tetracarboxylic dianhydride). The liquid crystal alignment agent of the present invention is preferably dissolved in the base-3 by the compound represented by the above formula (1) or the compound represented by the above formula (1') and the polyamic acid of the tetracarboxylic dianhydride and optionally added other components. -Aminotrimethoxy, etc. Epoxylated alcohol diglycidyl ether, 1,6-hexane dipentanediol di 3 glycol, (N,N-diglycidyl F amine, N,N - shrinkage The glyceryl)aminopropyl 'first liquid crystal substance, preferably, 'for the ''), is a compound of 30 weight: the resulting organic solvent -38-200832019 is prepared. When preparing the liquid crystal alignment agent of the present invention The temperature is preferably 〇 ° c to 200 ° C, more preferably 20 ° C to 60 ° C. As the organic solvent which can be used in the liquid crystal alignment agent of the present invention, for example, 1-methyl-2-pyrrolidone, r -butyrolactone, r-butyrolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4 Ketopentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol Ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl f.' k cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether Acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether acetate, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy- N,N-dimethylpropanamide, 3-hexyloxy-oxime, hydrazine-dimethylpropionamide, etc. Among them, 3-butoxy-indole, hydrazine-dimethylpropanamide, 3- Methoxy-oxime, Ν-dimethylpropanamide, 3-hexyloxy-oxime, Ν-dimethylpropanamide are particularly excellent in exhibiting good printability. & Solid in liquid crystal alignment agent of the present invention Component concentration (the weight after removing the solvent from all the components of the liquid crystal alignment agent and dividing by the total weight of the liquid crystal alignment agent) The viscosity is selected in consideration of viscosity, volatility, etc., preferably in the range of 1 to 10% by weight. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film as a liquid crystal alignment film, when solid When the concentration of the component is less than 1% by weight, the film thickness of the coating film is too small to obtain a good liquid crystal alignment film; and when the solid content concentration exceeds 10% by weight, the film thickness of the coating film is too thick, thereby A good liquid crystal alignment film cannot be obtained, and -39-200832019 may cause an increase in viscosity of the liquid crystal alignment agent, and the coating characteristics may be deteriorated. In addition, a particularly preferable range of solid content concentration is due to application of a liquid crystal alignment agent. The method used when applying the substrate differs. For example, in the case of using the spin coating method, it is particularly preferably in the range of 1 · 5 to 4 · 5 % by weight. When the printing method is used, the solid content concentration is in the range of 3 to 9 % by weight, whereby a particularly preferable solution viscosity is in the range of 12 to 50 mPai. When the ink jet method is used, the solid content concentration is in the range of 1 to 5 % by weight, whereby a particularly preferable solution viscosity is in the range of 3 to 15 m P a · s. F' _ % The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention. The liquid crystal display element of the present invention can be produced, for example, by the following method. (1) The liquid crystal alignment agent of the present invention is applied onto one surface of a substrate provided with a patterned transparent conductive film by a lithography method, a spin coating method or an inkjet printing method, and then coated by heating the coated surface. membrane. Here, as the substrate, for example, glass such as float glass or soda lime glass; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, and alicyclic ring can be used. A transparent substrate made of a plastic such as a polyolefin. As the transparent conductive film provided on one surface of the substrate, a NES film (registered trademark of PPG, USA) composed of tin oxide (S η Ο 2) and indium tin oxide (In2〇3 - SnOO) can be used. In the ITO film or the like, the pattern of forming the transparent conductive film is a photolithography method or a method in which a mask is used in advance. In order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film during the application of the liquid crystal alignment agent, Further, a functionalized-40-200832019 decane compound, a functional titanium-containing compound, or the like may be applied to the surface of the substrate. After the liquid crystal alignment agent is applied, it is preferably used to prevent liquid sag of the applied alignment agent. Pre-heating (pre-bake) is carried out. The pre-baking temperature is preferably from 30 to 200 ° C, more preferably from 40 to 150 ° C, particularly preferably from 40 to 100 ° C. Then, the solvent is completely removed. The calcination (post-bake) process is carried out for the purpose of the imidization of the polyglycolic acid. The calcination (post-baking) temperature is 80 to 300 ° C, preferably 1 2 0 2 5 (TC. In addition, the liquid crystal of the invention containing poly-proline The alignment agent is formed by removing the organic solvent to form a coating film as an alignment film, and may further perform dehydration ring closure by further heating to form a coating film which is further imidized. The film thickness of the formed coating film is formed. It is preferably 0.00 1 to 1 μηι, more preferably 0.005 to 0·5 μιη 〇 (2) The formed coating film surface is coated with a roll wrapped with a cloth composed of fibers such as nylon, rayon, cotton or the like. In the same manner, a liquid crystal alignment film in which the alignment property of the liquid crystal molecules is generated on the coating film is produced. Further, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is subjected to, for example, Patent Document 2 (Japanese Patent Laid-Open No.) The process of changing the pretilt angle by partially irradiating ultraviolet rays, or performing the patent, as shown in the Japanese Patent Laid-Open No. Hei 6-281-93 In the case of the liquid crystal alignment film which has been subjected to the rubbing treatment, a protective film is partially formed as shown in the document 4 (Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. After that, the protective film is removed, and the liquid crystal alignment of the liquid crystal alignment film can be changed, so that the field of view characteristics of the liquid crystal display element can be improved. (3) Two substrates having formed a liquid crystal alignment film are formed as described above -41 - 200832019 The two substrates are placed opposite each other with a gap (cell gap) so that the polishing directions of the respective liquid crystal alignment films are perpendicular or anti-parallel to each other, and the peripheral portions of the two substrates are bonded together with a sealant to the surface of the substrate and sealed. a liquid crystal cell is enclosed in the cell gap separated by the agent to form a liquid crystal cell. Then, the polarizing plate is attached to the outer surface of the liquid crystal cell, that is, the other side surface of each substrate constituting the liquid crystal cell. The liquid crystal display element was obtained by making its polarization direction coincide with or perpendicular to the rubbing direction of the liquid crystal alignment film formed on one side of the substrate. Here, as the sealant', for example, an alumina ball-containing epoxy resin as a curing agent and a gap can be used. Examples of the liquid crystal include a nematic liquid crystal and a dish-shaped liquid crystal. Among them, a nematic liquid crystal is preferable. For example, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, or a phenyl ring can be used. A hexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenylcyclohexane liquid crystal, a pyrimidine liquid crystal 'dioxanthene liquid crystal' bicyclooctane liquid crystal, a cuba liquid crystal, or the like. Further, in these liquid crystals, cholesteric liquid crystals such as cholesteryl cholesteryl, cholesteryl phthalate, and cholesteryl carbonate may be added, and under the trade names "C-15" and "CB-15" (manufactured by Merck) It is used by selling chiral agents and the like. Further, a ferroelectric liquid crystal such as p-nonyloxybenzylidene-p-amino-2-methylbutylcinnamate may also be used. In addition, a polarizing plate which is formed by sandwiching a polarizing film called a ruthenium film which is obtained by absorbing iodine while extending polyvinyl alcohol from the outer surface of the liquid crystal, is exemplified by a polarizing plate. Or a polarizing plate made of the diaphragm itself. [Examples] Hereinafter, the present invention will be more specifically described by way of examples. However, the invention is not limited to the examples. In the following examples and comparative examples, the evaluation of the liquid crystal alignment agent and the liquid crystal alignment film produced therefrom was carried out according to the following method Μ θ. [Voltage Retention Rate] A voltage of 5 V was applied to the liquid crystal display element at 6 〇 in a time interval of 167 ms. The voltage application time was 6 〇 microseconds, and then the voltage was released from the voltage release to 167 ms. Voltage retention rate. The measuring device used VHR-1 manufactured by Dongyang Technology Co., Ltd. Γ' [After image experiment] A cell with an IΤ 0 electrode as shown in Fig. 1 was produced. At room temperature, a DC voltage of 1 0 · 0 V was applied to the electrode crucible for 24 hours, and a DC voltage of 0.5 V was applied to the electrode crucible for 24 hours. After the voltage was released, 电极1 to 5.0 V DC voltage was applied to the electrodes a and B in a gradient of 11 v, and the residual image characteristics were judged by the difference in luminance between the electrodes a and B at the respective voltages. When the luminance difference is large, the afterimage characteristic is judged to be poor. No remnants were found as 〇, and afterimages were recorded as X. f [Printability evaluation] A 1 2 7 mm (D ) X 1 2 7 mm (W) x 1 · 1 mm (Η) glass substrate with an I Τ film formed on the entire surface of one side is prepared. The liquid crystal alignment agent prepared in the examples or the respective comparative examples was filtered with a microporous filter having a pore diameter of μ. 2 μηι, and then coated with a liquid crystal alignment film coating printing machine (manufactured by Japan Photographic Co., Ltd., Angstromer S-40L). Apply to the transparent electrode surface of the glass substrate. The solvent was removed by a hot plate-fitting pre-dryer set at 80 ° C, and baked at 200 ° C for 60 minutes to form a liquid crystal alignment film on a glass substrate with an ITO film. The unevenness of the obtained alignment film was visually evaluated, and no unevenness was reported as "〇". Synthesis Example 1 Synthesis Example 1 was carried out in accordance with Non-Patent Document 2 (K. Hasegawa, Polymer Journal. Vol. 31, No. 2, 206 (1999)). 2,7-dimethane 3.24 g (10 mmol) and p-phenylenediamine 2.16 g (20 mmol) were placed in a 300 mL three-necked flask under an aerobic environment, and then 80 mL of toluene was added thereto to dissolve. Then, to the solution, 5.8 g (60 mmol) of sodium butoxide, 0.36 g (0.5 mmol) of tris(dibenzylideneacetone)-dipalladium r · '(Pd2(dba)3) and 2,2'-bis(diphenylphosphino)-1,1'-dinaphthyl (fluorene) 0·9 3 g (1.5 mmol) was dissolved. The solution was stirred under nitrogen at 1 〇 ° C for 16 hours to cause a reaction. After completion of the reaction, the reaction mixture was returned to room temperature, and washed with a mixture of 2 liters of aqueous ammonia and methanol (ammonia/methanol = 1/4 (volume ratio)) using a separating funnel. The organic solvent layer was dehydrated with sodium sulfate, and concentrated by a rotary evaporator. The obtained crude product was purified by yttrium gel chromatography to obtain 2.2 g of the compound represented by the following formula (A-1) (hereinafter referred to as " Specific compound A - 1 ").

Synthesis Example 2 A synthesis example 1 was used except that 3.97 g (20 mmol) of 4,4'-diaminodiphenylmethane was used instead of 2 · 16 g (20 mm ο 1) of p-phenylenediamine in Synthesis Example 1. In the same manner, 2.4 g of a compound represented by the following formula (A-2) (hereinafter referred to as -44-200832019 "specific compound A-2") was obtained.

Synthesis Example 3

Except that in Synthesis Example 1, 3.12 g (10 mmol) of 4,4'-dibromobiphenyl was used instead of 3.24 g (10 mmol) of 2,7-dibromofluorene, and 3.97 g (20 mmol) of 4,4,-diamino group was used. In the same manner as in Synthesis Example 1, except that diphenylmethane was replaced by 2.16 g (20 mmol) of p-phenylenediamine, 4 2 g of a compound represented by the following formula (A-3) was obtained (hereinafter, referred to as "specific compound A - 3").

Synthesis Example 4 0.63 g (1.66 mmol) of the specific compound A-1 and 1.23 g (13.3 mmol) of epichlorohydrin were dissolved in a mixed solvent of 10 mL of THF and 1.5 mL of water, and stirred at 80 ° C for 4 hours. Then reduce the temperature to 60 °C, add lg 50%

Aqueous NaOH solution. After stirring at 60 ° C for 4 hours, the unreacted epichlorohydrin was removed by evaporation under reduced pressure. The residue was subjected to liquid separation washing in toluene/water, and then the solvent was distilled off to obtain 〇.75 g of the following formula (Β υ υ

Synthesis Example 5 (Synthesis of polylysine using a specific compound Α-1) i 196 g (1.0 mol) of 1,2,3,4-cyclobutanine tetracarboxylic dianhydride as tetracarboxylic dianhydride And 3 24 g (1.0 mol) as a diamine compound, the specific compound A~1 synthesized by the same method as in Synthesis Example 1-45-200832019 was dissolved in 470 g N-methyl-2-pyrrolidone In 4 2 0 0 gr - butyrolactone, it was reacted at 40 ° C for 3 hours to obtain a polypyrene having a solution viscosity of 1600 mPa.s at a solid concentration of 1 〇%. A solution of an amine acid (hereinafter referred to as "specific compound C-1"). Synthesis Example 6 (Synthesis 2 of Polylysine Using Specific Compound A-1) 98 g (0.5 mol) of iota, 2,3,4-cyclobutanetetracarboxylic dianhydride of tetracarboxylic dianhydride and 109 g (0.5 mol) of pyromellitic acid, and 324 g (l. oxime) as a C diamine compound, the specific compound A-1 synthesized by the same method as in Synthesis Example 1 was dissolved in 300 g N - In methyl-2-pyrrolidone and 2700 gr-butyrolactone, the reaction was carried out at 40 ° C for 3 hours, and then 1 7 7 gr -butyrolactone was added to obtain about 5100 g at a solid concentration of 10 The solution viscosity at % is a solution of 125 mPa, s poly-proline (hereinafter referred to as "specific compound c-2"). Synthesis Example 7 (Synthesis 1 of polylysine using specific compound a-3) 196 g (1.0 mol) of iota, 2,3,4-cyclobutane tetracarboxylate dianhydride as tetracarboxylic dianhydride And 5478 (1.0 mol) as a diamine compound, the specific compound A-3 synthesized by the same method as in Synthesis Example 3 was dissolved in 670 g of N-methyl-2-pyrrolidone and 6000 g of γ-butyrolactone. So that it can be reacted at 4 (Γ for 3 hours to obtain a solution of about 7000 g of polyamic acid (hereinafter, referred to as "specific compound c-3") having a solution viscosity of 140 mPa·s at a solid concentration of 10%. Synthesis Example 8 (Synthesis 2 of Polylysine using a specific compound a-3) 98 g (0.5 mol) of me-cyclobutane tetracarboxylic acid-46-200832019 acid dianhydride and 1 as tetracarboxylic dianhydride 0 9 g (0 · 5 mol) pyromellitic acid, and 5 4 7 g (1·0 mol) as a diamine compound, the specific compound Α 3 synthesized by the same method as in Synthesis Example 3 was dissolved in 430 g of hydrazine-methyl-2-pyrrolidone and 3850gr-butyrolactone were reacted at 40 ° C for 3 hours, and then 2,500 gr - butyrolactone was added to obtain about 72 OOg of solid content. A solution having a solution viscosity of 10% at 12 8 mPa·s of poly-proline (hereinafter referred to as "specific compound C-4"). Polyimine synthesis Example 1 2, 3 as tetracarboxylic dianhydride 5-tricarboxycyclopentyl acetic acid dianhydride 112g (0.50 mol) and 1,3,3a,4,5,9b-hexahydro·8-methyl-5-(tetrahydro-2,5-dioxo -3-furanyl)-naphthalene [l,2-c]furan-1,3-dione 157 g (0.50 mol), p-phenylenediamine as a diamine compound 96 g (0.89 mol), 3,3 '-(Tetramethyldioxane-1,3-diyl)di(propylamine) 25g (0.10 mole) and 3,6-bis(4-aminobenzylideneoxy)cholane 13g ( 0.02 0 mol), 8.1 g (0.03 mmol) of n-octadecylamine as a monoamine was dissolved in 960 g of N-methyl-2-pyrrolidone, and allowed to react at 60 ° C for 6 hours. The poly-proline solution was divided into small amounts, NMP was added, and the viscosity was measured in a solution having a solid concentration of 10%. The viscosity of the solution was 60 m P a · s. 2 700 g was added to the obtained poly-proline solution. N-methyl-2-pyrrolidone, adding 3 9 6 g of pyridine and 4 0 9 g of acetic anhydride, dehydration and ring closure at 1 1 ° C for 4 hours. After that, the solvent in the system was replaced with a new 7-butyrolactone (in this operation, the pyridine and acetic anhydride used in the oxime imidization reaction were removed to the outside of the system) to obtain about 2 Å. g The solid concentration of 15% by weight, the solid concentration of 1% by weight (7-butyrolactone solution), the solution viscosity of 7〇111?1, and the oxime imidization rate of about 95% of the yttrium-47-200832019 amine A polymer (which acts as a "polyimine (al)") solution. Polyimine synthesis example 2 224 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dioxime as tetracarboxylic dianhydride, p-phenylenediamine 10 g as a diamine compound (l. 〇mol) and 3,5-diaminobenzoic acid cholesteryl 7.8 g (0.015 mol) dissolved in 3 0 3 9 g N-methyl-2-pyrrolidone, making it at 6 The reaction was carried out at 0 ° C for 6 hours to obtain a polyaminic acid solution having a solution viscosity of about 260 mPa·s. Next, 2700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and ^3 9 6 g of pyridine and 3,6 g of acetic anhydride were added, and the mixture was dehydrated and closed at 110 ° C for 4 hours. After the imidization reaction, the solvent in the system is replaced with a new r-butyrolactone (in this operation, the pyridine and acetic anhydride used in the oxime imidization reaction are removed to the outside of the system) 3 000g of yttrium imidized polymer having a solid concentration of about 9.0% by weight, a solid concentration of 10% (r-butyrolactone solution), a solution viscosity of 25 0 mPa·s, and a ruthenium iodide ratio of about 51% ( It is used as a solution of the "indoleized polymer (a-2)"). Polylysine Synthesis Example 1 196 g (1.0 mol) of 1,2,3,4·cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride as 2,2'-di of diamine compound Methyl-4,4,-diaminobiphenyl 212g (l. oxime) was dissolved in 370g of N-methyl-2-indole ketone, 3300g r - butyrolactone, making it at 40 The reaction was carried out at ° C for 3 hours to obtain about 370 g of polylysine having a solution viscosity of 1 60 mPa·s at a solid concentration of 1% by weight (as "polylysine (b-1)") Solution. Polylysine Synthesis Example 2 1,2,3,4-cyclobutanetetracarboxylic dianhydride as a tetracarboxylic dianhydride -48-200832019 95g (0.50 mole), pyromellitic acid anhydride 9g (〇.5〇莫耳), 2,7-diaminopurine as a diamine compound, 196g (1.0m) dissolved in 23〇gN-methyl-2-hydroxypyrrolidone, 2 0 6 0 g τ - butyrolactone in 'make it at 4 〇. The reaction was carried out for 3 hours, and then 1,350 g of 2 r -butyrolactone was added to obtain about 3,600 g of polylysine having a solution viscosity of 1 2 5 m P a · s at a solid concentration of 10% (as a "poly" Amino acid (b-2)") solution. Example 1 Polyimine (a-1) prepared in Polyimine Synthesis Example 1 and Polylysine (b-1) prepared in Polyamine Synthesis Example 1 as Polyimine : Polyglycine = 2 0 : 8 0 (weight ratio) dissolved in γ - butyrolactone / N - methyl - 2 - pyrrolidone / butyl cellosolve mixed solvent (weight ratio 7 1 / 1 7 / 1 2 ) , adding 2 parts by weight of ruthenium, osmium, iridium, Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane relative to 100 parts by weight of polyimine and polyaminic acid And adding 10 parts by weight of the specific compound Α -1 to a solution having a solid concentration of 3.6 wt% and a solution of 6.0 wt% with respect to 1 〇 0 parts by weight of the total of the polyimine and the polyaminic acid. . After the respective solutions were thoroughly stirred, they were filtered through a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent of the present invention. A solution having a solid concentration of 3.5% in the above liquid crystal alignment agent was applied to a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm using a spin coater (rotation speed: 25) 00 rpm, coating time: 1 minute), the solvent was removed by heating at 200 ° C for 1 hour to form a coating film having a film thickness of 0.08 μm. The coating film was sanded using a grinding machine equipped with a roll of a woven fabric made of rayon, with a roll speed of 400 rpm, a table moving speed of 3 cm/sec, and a fluffing length of 0 · 4 mm. . After the ultra-pure liquid crystal alignment film-coated substrate of -49-200832019, the outer surface of the liquid liquid crystal alignment film of the bright electrode/transparent electrode substrate is dried in a clean oven at 1 ° C, except that the liquid crystal diameter is The epoxy crystal of the 5 · 5 μ m oxidized crystal ball is relatively heavy and combined with the film surface, and is filled with the liquid crystal injection port to the 歹MLC-6 22 1 ), and then sealed with acrylic light. Liquid crystal display element. In accordance with the voltage holding ratio of the liquid crystal display device, the printability evaluation was carried out by using the method described above for the solid content concentration. Examples 2 to 1 6 In addition to the specific compound, polyimine and the supported compound, the compound of the specific compound Cl, C-2, C-imine and polyglycolic acid was used in the same manner as in the examples. . Example 1 7 Mixing of a pyridyl-2-pyrrolidone/butyl cellosolve prepared in Polyimine Synthesis Example 2 Adding 7 Glyceryl-4,4,-diaminodiphenyl to 100 parts by weight of polyimine The methaneimine was added to 10 parts by weight of the specific compound water and ultrasonically washed for 1 minute and 10 minutes. Then, 'the coating of the pair of through-crystal alignment film-coated substrates is applied', and the resin adhesive agent' is then applied to cure the adhesive. Then, [J-type liquid crystal (Merck's production of 'curing adhesive' will be evaluated by the method described above for the liquid crystal injection port. The 6.0% by weight solution, according to the] polylysine use table The same procedure as described in 1 is carried out. When 3 or C is 4, 20 parts by weight of these tert-polyimine (a-2) is dissolved in N-methyl solvent relative to the polybenzal (weight) In the ratio of 5 0/ 5 0), the weight of N, N, N', N'-tetrahydration is further reduced to 100 parts by weight relative to 100 parts by weight of polyfluorene A - 1, and the solid concentration is -50-200832019. a solution of 5 wt% and a solution of 6.0% by weight. After thoroughly stirring each solution, the solution is filtered with a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent of the present invention. The evaluation method of the device and the evaluation method of the printability of the alignment agent were carried out in the same manner as in Example 1. Example 1 8 to 2 4 In addition to the use of the substance described in Table 1, the compound of the compound of Example 17 was replaced. Except for -1, the same procedure as in Example 17 was carried out. When compound C1, C-2, C-3 or C-4 is used, relative to 100 parts by weight of polyimine, 20 parts by weight of these specific compounds are used. 1 ° Comparative Examples 1, 2 except for polyimine and polyfluorene The amine was used in the same manner as in Example 1 except that the compound stomach described in Table 1 was used without adding a specific compound. Comparative Example 3 In the same manner as in Example 1 except that no specific compound was added, w The process is carried out. The results of the above examples and comparative examples are all listed in Table 1 ° and # ' Table 1, "1, which means that the component in the column is not used. In addition, the ' ® pressure retention rate is blocked. ">99%" means that the measured enthalpy exceeds 99%. -51 - 200832019 Table 1 Specific compound polyimine polyamine acid voltage retention rate image-printing Example 1 A-1 a-1 b-1 > 99% 〇〇 Example 2 A-2 a-1 b-1 > 99% 〇〇 Example 3 A-3 a-1 b-1 > 99% 〇〇 Example 4 B-1 a-1 b -1 >99% 〇〇Example 5 C-1 a-1 b-1 >99% 〇〇Example 6 C-2 a-1 b-1 >99% 〇〇Example 7 C-3 A-1 b-1 >99% 〇〇 Example 8 C-4 a-1 b-1 > 99% 〇〇 Example 9 A-1 a-1 b-2 > 99% 〇〇 Example 10 A-2 a-1 b-2 > 99% 〇〇 Example 11 A-3 a-1 b-2 > 99% 〇〇 Example 12 B — 1 a-1 b-2 > 99% 〇〇 Example 13 C-1 a-1 b -2 >99% 〇〇Example 14 C-2 a-1 b-2 >99% 〇〇Example 15 C 3-1 a-2 b-2 >99% 〇〇Example 16 C-4 A-1 b-2 > 99% 〇〇 Example 17 A-1 a-2 — > 99% 〇〇 Example 18 A-2 a-2 — > 99% 〇〇 Example 19 A-3 A-2 — > 99% 〇〇 Example 20 B — 1 a-2 — > 99% 〇〇 Example 21 C —1 a — 2 — > 99% 〇〇 Example 22 C-2 a— 2 - > 99% 〇〇 Example 23 C - 3 a-2 - > 99% 〇〇 Example 24 C - 4 a - 2 - > 99% 〇〇 Comparative Example 1 - a-1 b-1 >99% X 〇Comparative Example 2 - a-1 b-2 >99% X 〇Comparative Example 3 - a-2 - >99% X 〇-52- 200832019 [Simplified Schematic] Figure 1 Schematic diagram of the unit cell produced by the afterimage experiments of the examples and comparative examples.

Claims (1)

200832019 X. Patent application scope: 1. A liquid crystal alignment agent characterized by containing a compound represented by the following formula (1), R\ corpse N-Y-N-X-N-Y-N(1) R2 ABV (wherein, A and B are each independently a hydrogen atom or a glycidyl group, and R1 to R4 are each independently a hydrogen atom or a glycidyl group, and X is a divalent group represented by the following formula (XI) or (X2); ), (X1) (X2) Y is a divalent group represented by the following formula (Yl), (Y2) or (Y3), -54- 200832019 (wherein R5 to R14 are each independently a hydrogen atom, an alkyl group, an alkoxy group or a gas-containing courtyard group, and Z is a mono-, an NH-, a CH2-, a S〇2-, a C-CH3 ) 2 — or —C(CF3) 2 — represents a divalent group)). 2. The crystal alignment agent according to claim 1, wherein in the formula (1), γ is a divalent group represented by the above formula (Y1) or (Y2). 3. The liquid crystal alignment agent according to claim 1 or 2, wherein in the formula (1), A and B are a hydrogen atom, and R1 to R4 are each independently a hydrogen atom or a glycidyl group, but R 1 to R 4 At least one of them is a glycidyl group. Representation 4. A liquid crystal alignment agent' characterized by containing a polyamine R1 obtained by reacting a compound of the following formula (1, -55-200832019 with a tetracarboxylic dianhydride) 1 R2, / N - Y - N - X - N - Y - N (r) AB R1, ~ R4, is an alignment agent, the poly unit of the repeating unit (in the formula, A, B, X and Y and The above formula (1) is the same oxygen atom). 5. The liquid according to any one of claims 1 to 4, further comprising a polyphosphonic acid selected from the group consisting of the following formula (I-1) and having a weight represented by the following formula (I-2) At least one of the groups consisting of imines, HOOC, .COOH/Blowing CONH- (1-1) (wherein P1 is a tetravalent organic group, and Q1 is a divalent organic group), 200832019 (In the formula, P2 is a tetravalent organic group, and Q2 is a divalent organic group). {6> The liquid crystal alignment agent of claim 5, which comprises a polylysine having a repeating unit represented by the above formula (I-1) and a polyfluorene having a repeating unit represented by the above formula (I-2) An imine, and the polyamic acid and polyimine are synthesized from a tetracarboxylic dianhydride and a diamine containing 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. A liquid crystal display element characterized by having a liquid crystal alignment film formed of a liquid crystal alignment agent according to any one of claims 1 to 6 - 57-